The state of the art describes many different polyurethane foams, for example hot-cured flexible foam, cold-cure foam, ester foam, rigid PUR foam, rigid PIR foam and many more. The stabilizers used here have been developed to match the respective end use and usually display a significantly altered performance if they are used for producing other types of foam.
In the production of rigid polyurethane and polyisocyanurate foams, cell-stabilizing additives are used in order to obtain a fine-celled, uniform foam structure which is low in defects and thus exert a significant positive influence on the use properties of the rigid foam, in particular the thermal insulation capability. Here too, surfactants based on polyether-modified siloxanes are particularly effective and are therefore the preferred type of cell stabilizers. Since there are many different rigid foam formulations for different fields of application which meet the individual requirements which the cell stabilizer has to meet, polyether-siloxanes of a variety of structures are used. Thus, for example, the choice of blowing agent has influenced the development of new, optimized stabilizers. While EP 0570174 A1 (U.S. Pat. No. 5,169,872) still describes the production of rigid polyurethane foam using chlorofluorocarbons, further development extends through pure fluorinated hydrocarbons as blowing agents, as described in EP 0533202 A1 (CA 2078580), to pentane which is now the standard blowing agent, as described in EP 1544235 A1 (U.S. Pat. No. 7,183,330).
Flexible polyurethane foams are frequently produced using carbon dioxide as environmentally friendly blowing agent. EP 0797606 A1 (U.S. Pat. No. 5,525,640) and EP 1501889 A1 (U.S. Pat. No. 6,653,359) describe the stabilizers customarily used for this application. However, methylene chloride is still used as blowing agent in countries having less strict environmental regulations. EP 0694585 A2 (U.S. Pat. No. 5,492,939) describes stabilizers used in this case.
EP 0600261 (U.S. Pat. No. 5,321,051) is concerned with polysiloxane-polyoxyalkylene block copolymers which have different polyoxyalkylene blocks in the average molecule and are used as stabilizers for producing flexible polyurethane foams. The teaching according to the invention goes into very precise details of the composition of the polyoxyalkylene radicals represented in the average silicone-polyether copolymer in terms of their average molecular weights, their ethylene oxide/propylene oxide ratio and their individual, percentage proportions in the polyethers attached in the total matrix.
EP 0 585 771 A2 (U.S. Pat. No. 5,306,737) discloses that the polysiloxane-polyoxyalkylene block copolymers which represent particularly good foam stabilizers are characterized by a combination which can only be determined empirically of hydroxy-functional and end-capped polyoxyalkylene blocks of differing molecular weight and differing hydrophilicity or lipophilicity. Only a precisely matched ratio of hydrophilic, lipophilic and siliconophilic polymer blocks gives the stabilizer its optimum action in the respective application. Experience shows that fluctuations in the hydrophilic, lipophilic and siliconophilic components in the polysiloxane-polyoxyalkylene block copolymer caused by raw materials can give poorer compatibilization of the foam stabilizer with the reacting polyurethane matrix, which can hinder homogeneous distribution of the surfactant and subsequent migration to the interface in such a way that foam collapse is the direct consequence.
An as yet unpublished patent application DE 10 2007 055485.2 (WO 2009-065644) describes a process for preparing organomodified polysiloxanes whose siloxane chain is branched, in which a branched polysiloxane having terminal and/or lateral SiH functions is prepared in only one process step and is further functionalized by means of organic compounds, and also branched organomodified polysiloxanes prepared by this process and their use.
Most processes for preparing alkoxylation products (polyethers) make use of basic catalysts such as alkali metal hydroxides and alkali metal methoxides. The use of KOH is particularly widespread and has been known for many years. A usually low molecular weight, i.e. having a molecular weight of less than 200 g/mol, hydroxy-functional starter such as butanol, allyl alcohol, propylene glycol or glycerol is typically reacted with an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide or a mixture of various alkylene oxides in the presence of the alkaline catalyst to give a polyoxyalkylene polyether. The strongly alkaline reaction conditions in this living polymerization promote various secondary reactions. Rearrangement of propylene oxide into allyl alcohol which in turn functions as chain initiator and chain termination reactions form polyethers having a relatively broad molar mass distribution and unsaturated by-products. A method of determining the iodine number with which those skilled in the art are familiar is the method of Hanus, known as method DGF C-V 11 a (53) of the Deutsche Gesellschaft für Fette.
The iodine number in accordance with DGF C-V 11 a (53) indicates the concentration of double bonds in a defined weight of a material.
The disadvantages of the base-catalyzed alkoxylation doubtlessly also include the necessity of freeing the reaction products obtained of the active base by means of a neutralization step. Removal of the water formed in the neutralization by distillation and also removal of the salt formed by filtration are then absolutely necessary.
Apart from the base-catalyzed reaction, acid catalyses are also known for alkoxylation. Thus, DE 10 2004 007561 (US Patent Appl. Pub. 2007-185353) describes the use of HBF4 and of Lewis acids such as BF3, AlCl3 and SnCl4 in alkoxylation technology.
A disadvantage found in the acid-catalyzed polyether synthesis is the unsatisfactory regioselectivity in the ring opening of unsymmetrical oxiranes such as propylene oxide, which leads to polyoxyalkylene chains having some secondary and some primary OH termini being obtained in a manner which is not readily controlled. As in the case of the base-catalyzed alkoxylation reaction, a work-up sequence of neutralization, distillation and filtration is also indispensible here. If ethylene oxide is introduced as monomer into the acid-catalyzed polyether synthesis, the formation of dioxane as undesirable by-product has to be expected.
However, multimetal cyanide compounds or double metal cyanide catalysts, generally also referred to as DMC catalysts, are also frequently used as catalysts for preparing polyether alcohols. The use of DMC catalysts minimizes the content of unsaturated by-products, and in addition the reaction proceeds with a significantly higher space-time yield compared to the customary basic catalysts. The preparation and use of double metal cyanide complexes as alkoxylation catalysts has been known since the 1960s and is described, for example, in U.S. Pat. No. 3,427,256, U.S. Pat. No. 3,427,334, U.S. Pat. No. 3,427,335, U.S. Pat. No. 3,278,457, U.S. Pat. No. 3,278,458, U.S. Pat. No. 3,278,459. The ever more effective types of DMC catalysts which were developed in subsequent years and are described, for example, in U.S. Pat. No. 5,470,813 and U.S. Pat. No. 5,482,908 include, in particular, zinc-cobalt hexacyano complexes. Thanks to their extraordinarily high activity, only low catalyst concentrations are required for preparing polyetherols, so that the work-up step necessary for conventional alkaline catalysts, consisting of neutralization, precipitation and filtration of the catalyst, at the end of the alkoxylation process can be omitted. The alkoxylation products prepared using DMC catalysts have a much narrower molar mass distribution compared to products catalyzed by means of alkali. The high selectivity of the DMC-catalyzed alkoxylation is the reason for, for example, polyethers based on propylene oxide containing only very small proportions of unsaturated by-products.
The alkoxylation reaction carried out over DMC catalysts in direct comparison with alkali and acid catalysis is so advantageous in terms of the technical characteristics described that it has led to the development of continuous processes for preparing voluminous simple polyetherols which usually comprise only PO units. Thus, WO 98/03571 (U.S. Pat. No. 5,689,012) describes a process for the continuous preparation of polyether alcohols by means of DMC catalysts, in which a mixture of a starter and a DMC catalyst is firstly placed in a continuous stirred tank reactor, the catalyst is activated and further starter, alkylene oxides and DMC catalyst are introduced continuously into this activated mixture and, after the desired level of fill of the reactor has been reached, polyether alcohol is taken off continuously.
JP H6-16806 describes a process for the continuous preparation of polyether alcohols by means of DMC catalysts, likewise in a continuous stirred tank reactor or in a tube reactor in which an activated starter substance mixture is introduced at the inlet and alkylene oxide is fed in at various points along the tube reactor.
DD 203 725, too, describes a process for the continuous preparation of polyether alcohols by means of DMC catalysts, in which an activated starter substance mixture is introduced at the inlet of a tube reactor and alkylene oxide is fed in at various points along the tube reactor.
WO 01/62826 (U.S. Pat. No. 6,673,972), WO 01/62824 (U.S. Pat. No. 7,022,884) and WO 01/62825 (U.S. Pat. No. 6,664,428) describe specific reactors for the continuous process for preparing polyether alcohols by means of DMC catalysts.
In the case of the industrial processes described here, the patent literature places particular emphasis on the monodispersity of the polyetherol obtained by DMC processes. Thus, narrow molar mass distributions are often desirable, as in the case of the polyols utilized for PU foaming systems (DE 100 08630, U.S. Pat. No. 5,689,012).
As disclosed in U.S. Pat. No. 5,856,369 and U.S. Pat. No. 5,877,268, the high chemical purity and the high molar mass in combination with a low polydispersity of the unsaturated polyetherols prepared by means of DMC catalysts leads to highly active polyurethane foam stabilizers. However, the usability of the usually allyl alcohol-initiated polyetherols described in the field of PU foam stabilizers is restricted to a relatively small group of polyetherols which comprise ethylene oxide and propylene oxide monomer units in a sometimes randomly mixed sequence and in which the proportion of ethylene oxide must not be more than 60 mol % in order to avoid the formation of polyethylene glycol blocks in the polymer chain. To improve the solubility and thus the effectiveness of the stabilizers and also to strengthen the cell-opening action, the high molecular weight allyl polyethers which are disclosed in U.S. Pat. No. 5,856,369 and contain only 40% of ethylene oxide have to be used in combination with a molar excess of hydrophilic allylpolyethylene glycols. This restriction limits the universal usability of the relatively high molecular weight polyethers and the synthesis can be subject to fluctuations which are due to resulting incompatibilities and can lead to defective product performance or even to turbidity and phase separation (cf. copolymer 21 in U.S. Pat. No. 5,856,369).
Apart from universal usability in various formulations, the processing latitude is an important factor for determining the usefulness of a stabilizer. A wide processing latitude means that the foam properties remain constant in the event of fluctuations in the amount of starting materials introduced. The processing latitude can be determined by varying the amounts of stabilizer and catalyst used. As a person skilled in the art will know, highly active stabilizers such as the silicone-polyether copolymers described in U.S. Pat. No. 5,856,369 and U.S. Pat. No. 5,877,268 usually have a processing latitude which is too low. The patents U.S. Pat. No. 5,856,369 and U.S. Pat. No. 5,877,268 demonstrate that the use of particularly long-chain polyethers in the polyoxyalkylene part of the silicone-polyethercopolymer leads to relatively high-viscosity products which firstly have to be diluted with solvents in order to ensure normal handling.
Replacement of the polyetherols prepared by conventional alkaline catalysis by ones which have been synthesized by DMC catalysis thus gives different types of alkoxylation products whose usability as copolymer components in established silicone-polyether copolymers employed in polyurethanes is possible only to a limited extent.
To match the polyethers prepared by means of DMC catalysts to the polyetherols prepared by conventional alkaline catalysis for the purposes of making replacement easier, DE 10 2007 057145.5 (US Patent Appl. Pub. 2009-137751) teaches a method of controlling the molar mass distribution in the alkoxylation of hydroxyl compounds by epoxide monomers in the presence of double metal cyanide catalysts using specific hydrogensiloxanes and silanes which have at least one hydridic hydrogen atom bound directly to the silicon atom as additives. However, this document does not demonstrate the usability of the polyether compounds prepared with an increase in the polydispersity as copolymer components in silicone-polyethers, either in those having a branched siloxane chain or in those of the linear, laterally modified type, e.g. for flexible polyurethane foam systems.
It is an object of the present invention to prepare universally usable silicone-polyether block copolymers which have a balanced property profile in respect of their processability and ability to be formulated and a broad processing latitude and whose performance is comparable with and/or even superior to that of the established silicone-polyether copolymers.
It has now surprisingly been found that the object of the invention is achieved by preparing branched polysiloxanes having terminal and/or lateral SiH functions in only one process step or organomodifying linear polysiloxanes having lateral and/or terminal SiH functions by means of polyethers or polyether mixtures, wherein the individual polyethers of the mixture have a polydispersity Mw/Mn in the range from 1.0 to 1.5 and/or ratios Mn/MWIN and Mw/MWIN in the range from 0.7 to 1.3.
Since neutralization and also a possible subsequent methylation or acetylation of an allyl polyether can lead to buildup or degradation of unsaturated by-products, the iodine number of an allyl polyether is not directly related to its polydispersity.
Assuming that each allyl-initiated polyether chain contains only one double bond, the average molecular weight of the polyether can be calculated from the iodine number. If the proportion of unsaturated by-products in the polyether increases, the iodine number likewise increases. Especially when allyl alcohol is used as starter alcohol, the alkoxylation reaction carried out under alkaline catalysis also produces propenyl polyethers. These propenyl polyethers prove to be unreactive by-products in the hydrosilylating further processing to form SiC-bonded silicone-polyether copolymers and are also, due to the hydrolytic lability of the vinyl ether bond present in them and liberation of propionaldehyde, an undesirable source of odorous impurities in the product. This is described, for example, in EP 1 431 331 A1 (US 2004-0132951).
The iodine number is thus an indication of the number of hydrosilylatable chains in the total composition of the polyether, while, secondly, the polydispersity reflects the chain length distribution in the total composition, regardless of whether these chains are hydrosilylatable or not.
It has thus surprisingly been possible to discover a distinguishing criterion which allows the usability of allyl polyethers for the preparation of industrially advantageous polyurethane foam stabilizers to be predicted.
According to the teachings of U.S. Pat. No. 5,856,369 and U.S. Pat. No. 5,877,268, small molar proportions of frequently less than 10 mol % and not more than 33 mol % of high molecular weight hydrosilylatable allyl polyethers (MW greater than 5000 g/mol or even 7000 g/mol) in a total polyether composition having a molecular weight of the mixture of from 1100 to 3000 g/mol lead to the objective of preparing polyurethane foam stabilizers. Due to the proportion of high molecular weight allyl polyether, it is necessary here to carry out blending with a very short-chain, low molecular weight polyether having a molecular weight of only 500-800 g/mol, which can result in inhomogeneities and incompatibility problems.
These teachings are contradicted by the present inventive observation that the molecular weight of the polyethers is not alone a sufficient criterion and even relatively large molar proportions of over 16 mol % and in particular over 35 mol % of relatively high molecular weight polyethers can be introduced into a formulation as long as these polyethers meet the criterion in respect of the ratios of Mn and Mw to the iodine number.
Thus, even polyethers having a “similar” molecular weight can be converted into polyurethane foam stabilizers with the expectation of success. The polyether blend according to the invention for the preparation of hot-cure flexible polyurethane foam stabilizers preferably contains at least 16 mol % and in particular at least 35 mol % of the relatively high molecular weight component having an average molecular weight of greater than or equal to 3000 g/mol.
A person skilled in the art would find it surprising and in no way foreseeable that modification of a silicone skeleton by means of a polyether or a polyether combination would lead to the objective of the desired foam stabilizing action, e.g. in hot-cure flexible polyurethane foam systems, only when all polyethers used have a molar mass distribution in the range from 1.0 to 1.5. Components which additionally have the ratios Mn/MWIN and Mw/MWIN of the polyethers used in the range from 0.7 to 1.3 are particularly suitable.
According to these teachings according to the invention, the polyethers used should be selected not only with regard to their average molecular weights, their ethylene oxide/propylene oxide ratio and their individual, percentage proportions in the polyethers attached in the total matrix but also with regard to their polydispersity. Thus, the polydispersity, i.e. the measure of the molar mass distribution, in polyoxyalkylene compounds is to a large extent dependent on and determined by the type of catalysis and the reaction parameters in the preparation of the polyoxyalkylene compounds.
The invention provides silicone-polyethercopolymers of the formula (I)
                where        n and n1 are each, independently of one another, from 0 to 500, preferably from 10 to 200, in particular from 15 to 100, and (n+n1) is <500, preferably <200, in particular <100,        m and m1 are each, independently of one another, from 0 to 60, preferably from 0 to 30, in particular from 0.1 to 25, and (m+m1) is <60, preferably <30, in particular <25,        k is from 0 to 50, preferably from 0 to 10, in particular from 1 to 7,        R is at least one radical from the group consisting of linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having from 1 to 20 carbon atoms, preferably a methyl radical, with particular preference being given to all radicals R being methyl radicals,        R1 is R or R3,        R2 is R or a heteroatom-substituted, functional, organic, saturated or unsaturated radical, preferably a radical selected from the group consisting of alkyl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloxyaryl, acryloxyalkyl, methacryloxyalkyl, methacryloxypropyl and vinyl radicals, particularly preferably a methyl, chloropropyl, vinyl or methacryloxypropyl radical,        R3 is R and/or                    CH2—CH2—CH2—O—(CH2—CH2O—)x—(CH2—CH(R′)O—)y—(SO)z—R″            CH2—CH2—O—(CH2—CH2O—)x—(CH2—CH(R′)O—)y—R″            CH2—RIV             CH2—CH2—(O)x′—RIV             CH2—CH2—CH2—O—CH2—CH(OH)—CH2OH                        
                                    CH2—CH2—CH2—O—CH2—C(CH2OH)2—CH2—CH3,            where            x=0 to 100, preferably from 0 to 50,            x′=0 or 1,            y=0 to 100, preferably from 0 to 50,            z=0 to 100, preferably from 0 to 10,            R′ is an alkyl or aryl group which has from 1 to 12 carbon atoms and is unsubstituted or substituted, for example by alkyl radicals, aryl radicals or haloalkyl or haloaryl radicals, and            R″ is a hydrogen radical or an alkyl group having from 1 to 4 carbon atoms, a —C(O)—R′″ group where R′″=alkyl radical, a —CH2—O—R′ group, an alkylaryl group, e.g. a benzyl group, the —C(O)NH—R′ group,            RIV is a hydrocarbon radical which has from 1 to 50, preferably from 9 to 45, more preferably from 13 to 37, carbon atoms and is unsubstituted or substituted, e.g. by halogens,            SO is a styrene oxide radical —CH(C6H5)—CH2—O—,                        
with the proviso that at least one substituent from among R1, R2 and R3 is not R and that at least one substituent from among R1, R2 and R3 is a polyether which has a polydispersity Mw/Mn in the range from 1.0 to 1.5 and/or ratios Mn/MWIN and Mw/MWIN in the range from 0.7 to 1.3. The various monomer units of the siloxane chain and also of the polyoxyalkylene chain can be arranged in blocks or be randomly distributed.
Particular preference is given to silicone-polyether copolymers of the formula (I) in which k is from 1 to 7 and R1 is different from R.
The indices in the formulae shown here and the value ranges given for the indices are therefore the averages of the possible statistical distribution of the actual isolated structures and/or mixtures thereof.
The invention further provides compositions or mixtures of the silicone-polyether copolymers according to the invention of the formula (I) with one another and mixtures of the foam stabilizers according to the invention with further additives, for example nucleating agents, i.e. cell-refining additives, cell openers, crosslinkers, emulsifiers, flame retardants, antioxidants, antistatics, biocides, colour pastes, solid fillers, and/or with amine catalysts, metal catalysts and/or buffer substances.
The silicone-polyether block copolymers according to the invention of the formula (I) are particularly suitable as polyurethane foam stabilizers in fields of application such as flexible polyurethane foam, viscoelastic flexible foam, rigid polyurethane foam, cold-cure polyurethane foam, ester foam or high resilience foam (HR foam).
The polyurethane foams produced using the silicone-polyether block copolymers of the invention are particularly suitable for producing, for example, polymer articles containing polyurethane foams, e.g. furniture upholstery, refrigerator insulation, spray foams or metal composite elements for (structural) insulation, and also polymer articles which consist essentially of the polyurethane foam, e.g. mattresses or automobile seats; the listings are to be considered to be overlapping and not to be exhaustive.
The invention likewise provides blends or compositions of the silicone-polyether copolymers according to the invention of the formula (I) with solvents such as glycols, alkoxylates, carbonates, ethers, esters, branched and linear aliphatic and aromatic hydrocarbons or oils of synthetic and/or natural origin.
The polysiloxane-polyoxyalkylene block copolymers which form the basis of the invention can be prepared by noble metal-catalyzed hydrosilylation of the linear or branched hydrogensiloxanes of the formula (II) by means of allyl polyethers which are prepared, for example, as described in EP 1 520 870 (US Patent Appl. Pub. 2005-075468),
                where        n and n1 are each, independently of one another, from 0 to 500, preferably from 10 to 200, in particular from 15 to 100, and (n+n1) is <500, preferably <200, in particular <100,        m and m1 are each, independently of one another, from 0 to 60, preferably from 0 to 30, in particular from 0.1 to 25, and (m+m1) is <60, preferably <30, in particular <25,        k is from 0 to 50, preferably from 0 to 10, in particular from 1 to 7,        R is at least one radical from the group consisting of linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having from 1 to 20 carbon atoms, preferably a methyl radical, with particular preference being given to all radicals R being methyl radicals,        the radicals R4 are each, independently of one another, hydrogen or R,        the radicals R5 are each, independently of one another, hydrogen or R,        the radicals R6 are each, independently of one another, hydrogen, R or a heteroatom-substituted, functional, organic, saturated or unsaturated radical, preferably a radical selected from the group consisting of alkyl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloxyaryl, acryloxyalkyl, methacryloxyalkyl, methacryloxypropyl and vinyl radicals, particularly preferably a methyl, chloropropyl, vinyl or methacryloxypropyl radical,        
with the proviso that at least one substituent among R4, R5 and R6 is not R.
The hydrogen siloxanes used in the preparation of the polysiloxane-polyoxyalkylene block copolymers can likewise be prepared as described in the prior art, for example in EP 1439200 B1 (US Patent Appl. Pub. 2004-147703) and in the as yet unpublished patent application DE 10 2007 055485.2 (WO 2009-065644). The unsaturated polyoxyalkylenes used can be prepared by the literature method of alkaline alkoxylation of allyl alcohol or using DMC catalysts as described in the prior art, for example in DE 10 2007 057145.5 (US 2009-137751).
The polyurethane foams according to the invention can be produced using formulations and methods known from the prior art with in each case foams produced in parallel with addition of established foam stabilizers as reference.
The polyurethane foam can be produced in combination with water, methylene chloride, pentane, alkanes, halogenated alkanes, acetone or carbon dioxide as preferred physically acting blowing agents.
Further subjects of the invention are characterized by the contents of the claims, whose contents are fully incorporated by reference into the disclosure content of the present description.
The foam stabilizers according to the invention and their use are described by way of example below without the invention being restricted to these illustrative embodiments. Where ranges, general formulae or classes of compounds are indicated below, these are intended to encompass not only the ranges or groups of compounds which are explicitly mentioned but also all subranges and subgroups of compounds which can be obtained by leaving out individual values (ranges) or compounds. Where documents are cited in the present description, their contents are fully incorporated by reference into the disclosure content of the present invention.